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United States Patent 3 126 280 NOVEL PHoToGRAPIiIcPRoDUcTs, PROCESSES AND COMPOSITIONS EMPLOYING ANTHRA- PYRIDONE DEVELOPERS iElkan'R. Blout, Belmont, Sidney Kasman, Arlington, and

This invention relates to photography and more particularly to products, compositions and processes for the development of photosensitive silver halide elements.

It is one object of the present invention to provide novel processes and compositions for the development of silver halide emulsions, in which novel colored silver halide developing agents are used.

Another object is to provide novel processes and compositions for the development of silver halide emulsions, in which the novel silver halide developing agent is capable of developing an exposed silver halide emulsion and imparting a reversed or positive colored image of the developed image to a superposed image-receiving material.

Further objects are to provide said novel silver halide developing agents, and novel products, processes and compositions suitable for use in preparing monochromatic and multichromatic photographic images by the employment of said novel silver halide developing agents.

Other objects of the invention will in part be obvious and will in part appear hereinafter.

The invention accordingly comprises the processes involving the several steps and the relation and order of one or more of such steps with respect to each of the others, and the products and compositions possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.

The objects of this invention may be accomplished by the use of certain novel dyes which have the ability to develop an exposed silver halide emulsion; thus these dyes may be referred to as dye developers. These novel dyes or dye developers will be further described hereinafter.

The dye developers and the photographic processes and compositions disclosed herein are particularly usfeul in the treatment of an exposed silver halide emulsion, whereby a positive dye image may be imparted to another element, herein referred to as an image-carrying or image-receiving element.

U.S. Patent No. 2,983,606, issued May 9, 1961, to Howard G. Rogers, discloses dilfusion transfer processes wherein a photographic negative material, such as a photo graphic element comprising an exposed silver halide emulsion, is developed in the presence of a dye developer to impart to an image-receiving layer a reversed or positive dye image of the developed image by permeating into said emulsion a suitable liquid processing composition and bringing said emulsion into superposed relationship with an appropriate image-receiving layer. The inventive concepts herein set forth provide novel dye developers which may be advantageously used in such processes.

In carrying out the process of this invention, a photosensitive element containing a silver'halide emulsion is exposed and wetted with a liquid processing composition, for example, by immersing, coating, spraying, flowing, etc., in the dark, and the photosensitive element superposed prior to, during or after wetting, on an image-receiving element. In a preferred embodiment, the photosensitive element contains a layer of dye developer, and the liquid processing composition is applied to the photosensitive element in a uniform layer as the photosensitive "ice element is brought into superposed position with an image-receiving element. The liquid processing composition permeates the emulsion to provide a solution of dye developer substantially uniformly distributed therein. As the exposed silver halide emulsion is developed, the oxidation product of the dye developer is immobilized or precipitated in situ with the developed silver, thereby providing an imagewise distribution of unoxidized dye developer dissolved in the liquid processing composition. This immobilization is apparently due, at least in part, to a change in the solubility characteristics of the dye developer upon oxidation, and especially as regards its solubility in alkaline solutions. It may also be due, in part, to a tanning efiect on the emulsion by the oxidized developing agent. At least part of this imagewise distribution of unoxidized dye developer is transferred, by imbibition, to a superposed image-receiving layer. The image-receiving layer receives a depthwise diffusion, from the emulsion, of unoxidized dye developer, without appreciably disturbing the imagewise distribution thereof, to provide a reversed or positive, colored image of the developed or negative image. The image-receiving element may contain agents adapted to mordant or otherwise fix the diffused, unoxidized dye developer. lrnbibition periods of approximately one minute have been found to give good results, but this contact period may be adjusted where necessary to compensate for variations in temperature or other conditions. The desired positive image is revealed by separating the image-receiving layer from the silver halide emulsion at the end of the imbibitio'n period.

The dye developers of this invention may be utilized in the photosensitive element, for example in, on or behind the silver halide emulsion, or they may be utilized in the image-receiving element or in the liquid processing composition. In a preferred embodiment, a coating or layer of the dye developer is placed behind the silver halide emulsion, i.e., on the side of the emulsion adapted to be located most distant from the photographed subject when the emulsion is exposed and preferably also adapted to be most distant from the image-receiving layer when in superposed relationship therewith. Placing the dye developer behind the emulsion layer, as in the pre ferred embodiment, has the advantage of providing increased contrast in the positive image, and also minimizes any light-lilterin action by the colored dye developer. In this preferred embodiment, the layer of dye developer may be applied by using a coating solution containing, e.g., about 0.5 to 8%, by weight, of the dye developer. Similar concentrations may be used if the dye developer is ptilized as a component of the liquid processing cornposition. In an especially useful mode of disposing the dyedevelopers in the photosensitive elements, the dye developer is dissolved in a water-immiscible solvent and then dispersed in a gelatin coating solution.

The liquid processing composition which is used in the processes herein disclosed comprises at least an aqueous solution of an alkaline compound, for example, diethylamine, sodium hydroxide or sodium carbonate, and may contain the dye developer. In some instances, it may contain an additional silver halide developing agent. If the liquid processing composition is to be applied to the emulsion by being spread thereon, preferably in a relatively thin, uniform layer, it may also include a viscosityincreasing compound constituting film-forming material of the type which, when spread over a water-absorbent base, will form a relatively firm and relatively stable film. A preferred film-forming material is a high molecular weight polymer such as a polymeric, water-soluble ether inert to an alkali solution, as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose. Other film-forming materials or thickening agents whose ability to increase viscosity is susbtantially unaffected when left in solution for a long period of time may also be used.

The novel dye developers herein contemplated contain an anthrapyridone, that is, a 3-azabenzanthrone, nucleus to which is attached at least one and preferably not more than two organic groups capable of functioning as silver halide developing groups.

The novel dye developers of the present invention comprise anthrapyridone dyes characterized in that they contain at least one group of the formula:

wherein Y is a covalent bond or a divalent radical and Z is an aryl nucleus selected from the group consisting of benzene and naphthalene nuclei so substituted by at least two groups selected from the group consisting of hydroxyl and amino groups as to be capable of developing an exposed silver halide emulsion.

In addition to the substituents which provide the silver halide developing function, Z may be substituted by halogen, alkoxy, alkyl, etc., radicals. The term amino as used herein is intended to include amino groups so substituted as not to impair their respective silver halide developing function, for example, suitably substituted alkylamino and arylamino groups.

The novel compounds of this invention, as noted above, are dye developers which contain an aryl nucleus selected from the group consisting of benzene and naphthalene nuclei so substituted by at least two groups selected from the group consisting of hydroxyl and amino groups as to be capable of developing an exposed silver halide emulsion. A preferred silver halide developing group comprises a hydroquinonyl group. Other suitable developing groups include ortho-dihydroxyphenyl and orthoand para-amino substituted hydroxyphenyl groups. In general, the developing group comprises a benzenoid developing configuration, that is, an aromatic developing group which forms quinonoid or quinone products upon oxidation.

As examples of divalent radicals, signified by the term Y and suitable for use in the practice of the present invention, mention may be made of: divalent organic radicals such as alkylene radicals, preferably lower alkylene radicals such as ethylene, isopropylene, etc.; sulfonarnido; sulfamyl; carboxamido; carbamyl, arylene radicals such as phenylene, etc.; aralkylene radicals such as phenethyl, etc.; acyl radicals such as if Q-alkylene-C- etc.; divalent radicals which contain both hetero and carbon atoms as constituent components, as for example,

etc.; and suitable combinations thereof.

The anthrapyridone dye developers may be represented by the formula:

wherein 2 Each of R R R R R, R", R and R may beYZ,

hydrogen, aryl, alkyl and preferably lower alkyl, halogen, amino, cyano, acyl, nitro, carboalkoxy, carboxyl, sulfo, alkoxy, hydroxyl, carboxamido, or aralkyl;

R may be YZ, hydrogen, alkyl and preferably lower alkyl, aryl or aralkyl;

YZ has the same significance as previously noted;

at least one developing group YZ is present;

and wherein more than one developing group YZ is present, each such group YZ may be the same or different.

As herein used, the terms amino, alkyl, aryl, etc. are intended to include the corresponding substituted groups. Thus, amino is intended to include groups such as methylamino and anilino, alkyl is intended to include groups such as aminomethyl and fl-hydroxyethyl, etc.

A preferred group of anthrapyridone dye developers may be represented by the formula:

wherein R is hydrogen or an acetyl radical; and each of R and R may be hydrogen, a lower alkyl such as methyl, ethyl, isopropyl, etc., or YZ, where Y is a divalent organic linking group selected from the group consisting of lower alkylene, sulfonamido, sulfamyl, carboxamido, carbamyl, phenylene,

0 ll lower alkylene, @lower alkylene-C- t I-lowcr alkylcne-S, 0-, fi- O radicals; and Z is an aryl nucleus selected from the group consisting of benzene and naphthalene nuclei substituted by two groups selected from the group consisting of hydroxyl and amino groups, one of said groups being substituted in one of the ortho and para positions with respect to the other of said groups so as to be capable of developing an exposed silver halide emulsion, and at least one of said R and R is -YZ.

As examples of useful anthrapyridone dye developers within the scope of the last-mentioned formula, mention may be made of the following compounds:

W3 I I 6 0E h h' met yl ant rapyr W1th1n the preferred group,wh1ch have a6-a1kylam1n0 01' 6-arylamino substituent, are magenta dye developers having exceptionally good spectral characteristics, since they 0 40 absorb only a minimal amount of light which ideally H CH3 should be transmitted. Thus,'these dye developers are particularly useful in multicolor products and processes such are described in the aforementioned U.S. Patent No.

l 2,983,606. Moreover, those analogues having a 6-aryl- OH v amino substituent have been found to possess unusually good stability. It Will'be appreciated that the alkylamino or arylaminosubstituent may in turn be substituted, as

V illustrated in the above-named compounds, and may, for

(1)11 g 1|\IHOH? OH2- example, contain a developing function.

As examples of other anthrapyridone dye'developers,

I OH

I N- H-CHz mention maybe made of the'following compounds:

dihydroxyphenyl) -a-methyl] -ethylamino-anth rapyridone anthrapyridone O NH CHg--CH2 dihydroxyphenyl) -ethy1] -anili11o-nnthrapyrimidone The anthrapyridone dye developers of this invention may be prepared by methods similar to those used to prepare anthrapyridone dyes. Thus, the anthrapyridone dye developers may be synthesized by cyclization of 1- acetamidoanthraquinones, the acetyl group of which may be unsubstituted or substituted, for example, preferably substituted with a halogen group such as chlorine, by ester condensations with anthraquinones having a primary or secondary amino group alpha to a. carbonyl group, e.g., l-aminoanthraquinone, or by cyclization of suitably substituted benzoic acids, e.g., m-carboxyanilides or phenylpropiolic acid, phenylpropionic acid or phenylpropargylic acid. The desired developer group or groups X may be introduced before or after formation of the anthrapyridone nucleus, as illustrated in Examples 1 and 2, respectively. It will be apparent that various groups may be substituted before or after formation of the anthrapyridone nucleus for the purpose of modifying the color, solubility, or other properties.

One preferred method of preparing the aforementioned anthrapyridone dye developers wherein the desired developer group or groups is introduced prior to formation of the anthrapyridone nucleus comprises condensing an anthraquinone dye having at least one group of the formula:

H l l-Y-Z wherein Y and Z have the same significance as previously set forth; substituted on the anthraquinone nucleus in aposition to a carbonyl group with an ester selected from the group consisting of acetoacetic, malonic and cyanoacetic esters.

The aforementioned ester condensations are preferably effected in the presence of a suitable catalyst, as for example, a mixture of sodium acetate and cuprous chloride.

Another preferred method of preparing anthrapyridone dye developers wherein the desired developer group or groups is introduced prior to formation of the anthrapyridone nucleus comprises acetylating an anthraquinone dye developer having a secondary amino group, such as the aforementioned this treatment concurrently acetylates the developing group. The cyclization may be carried out, for example, by refluxing with an alkaline solution in an inert atmosphere, such as under a blanket of nitrogen. The acetylated developer group is hydrolyzed to the free developer during this cyclization.

A preferred method of preparing the aforementioned anthrapyridone dye developers wherein the desired developer group or groups is introduced subsequent to formation of the anthrapyridone nucleus comprises reacting an anthrapyridone dye having a nitro or halogen group substituted in position 6 with a compound of the formula:

wherein Y has the same significance as previously noted, X represents a primary or secondary amino group, and Z represents a protected developer group, e.g., 2',5'- diacyloxyphenyl, etc.

Another method of preparing the aforementioned anthrapyridone dye developers comprises effecting a condensation reaction between an anthrapyridone dye having substituted thereon one or more sulfonyl chloride and/or acid chloride groups and a compound within the lastmentioned formula.

As an example of the last-mentioned anthrapyridone dye intermediates, mention may be made of the sulfonyl chloride derivative of As examples of compounds within the aforementioned formula XYZ, mention may be made of the followmg:

Amino-ethyl-hydroquinone, the preparation of which is disclosed in the copending US. application of Milton Green, Serial No. 514,095, filed June 8, 1955;

Amino-phenethyl-hydroquinone, the preparation of which is disclosed in the copending US. application of Elkan R. Blout, Milton Green, Howard G. Rogers, Myron S. Simon and Robert B. Woodward, Serial No. 612,051, filed September 25, 1956; and in a continuation-in-part thereof, Serial No. 98,287, filed March 27, 1961;

Amino-phenethyl-thio-hydroquinone, the preparation of which is disclosed in the copending U.S. application of Milton Green and Howard G. Rogers, Serial No. 663,876, filed June 6, 1957;

Amino-phenoxy-hydroquinone, the preparation of which is disclosed in the copending US. application of Milton Green and Warren E. Solodar, Serial. No. 680,406, filed August 26, 1957;

Amino-propyl-amino-hydroquinone, the preparation of which is disclosed in the copending U.S. application of Milton Green and Myron S. Simon, Serial No. 711,812, filed January 29, 1958; and

Amino-hydroquinone, amino-phenyl-hydroquinone, and amino-phenyl-sulfonyl-hydroquinone, etc., which may be prepared by known chemical reactions.

In addition, the aforementioned anthrapyridone dye developers may be prepared by effecting a condensation reaction between an anthrapyridone dye having substituted thereon one or more primary and/or secondary amino groups and a compound of the formula:

wherein Y and Z have the same significance as previously noted and W represents an acid chloride or sulfonyl chloride group.

The enumeration and preparation of compounds within the last-mentioned formula are set forth in the following copending US. applications:

Serial No. 471,542, filed November 26, 1954, in the names of Elkan R. Blout, Saul G. Cohen, Milton Green, Howard G. Rogers, Myron S. Simon, and Robert B.

9 Woodward, and in Serial No. 1,442 and l,443,'both filed January 11, 1960, and each a continuation-impart thereof; and

Serial No. 771,718, filed November 4, 1958, in the names of Elkan R. Blout and Richard S. Corley, and now abandoned.

It may be desirable to protect the hydroxyl and/or amino groups of the developing function, during the above-mentioned reactions, to avoid undesirable .side reactions, that is to employ a protected derivative of Z. The protected derivatives of Z set forth 'in formula X-Y-Z may be prepared by the selective acylation of Z according to the procedure disclosed in the copending US. application of Milton Green and Helen P. Husek, Serial No. 612,063, filed September 25, 1956, and which was abandoned in favor of Serial No. 805,673, filed April 13, 1959. The protected derivatives of Z set forth in formula WY-Z may be prepared by conventional acylation of Z according to procedures Well known to the art. After reaction and prior to use as a photographic dye developer, the acyloxy groups may be removed by deesterification as, for example, by hydrolysis in the presence of alkali.

The following examples show by Way of illustration and not by way of limitation the preparation of novel dye developers within the scope of this invention Example 1 1,4 bis [Q (2',5' dihydroxyphenyl)-ethylamino]- anthraquinone is heated in quinoline, under nitrogen, with 3 to 4 equivalents of acetoacetic ester at 190 C., in the presence of sodium acetate and a small amount of cuprous chloride. The reaction mixture is agitated occasionally. After 5 to 6 hours, the reaction mixture is treated with excess 10% hydrochloric acid. The residue is dissolved in methyl Cellosolve from which the product is precipitated by addition of Water. Reprecipitation from methyl Cellosolve with benzene yields the desired anthrapyridone dye developer, 1-acetyl-3-p- (2,5-dihydroxyphenyl) ethyl 6 6 (2',5'-dihydroxyphenyl)-ethylamino-anthrapyridone of the structure:

on 0 El) II fi-om-om whose spectral absorption curve in ethanol exhibits absorption maxima at 514 m x and 545 m Example 2 24.2 g. (.10 mole) of leucoquinizarin, 60.0 g. (.225 mole) of amino-phenethyl-hydroquinone hydrochloride, 12.4 g. (.2 mole) of boric acid, 21.0 g. (.25 mole) of sodium bicarbonate, and 250 ml. of methyl Cellosolve were mixed together and refluxed under a blanket of nitrogen for about 20 hours with stirring. 24.6 g. .1 mole) of practical grade chloranil was then added and refluxing was continued until oxidation was complete. The mixture was then cooled, filtered, and the filtrate poured into excess dilute hydrochloric acid to yield a precipitate. This precipitate was filtered off, rinsed with cold water and dried to yield 56.1 g. of'a cyan dye developer, 1,4 bis [4 [3 (2",5" dihydroxyphenyl) ethyl]- anilino-anthraquinone, having a melting point of 205 10 C., exhibiting a spectral absorption curve in ethanol having a A of 652 my. and 607 m e=17,000, and having the following structural formula:

I Nrrornorn 0 H on [I I o NH-Q-Clilz-OH 33.2 g. (.05 mole) of the above compound and 600 ml. of benzene were refluxed through a water trap until dry. The trap was removed and 0.5 ml. of pyridine and the 55 ml. (.77 mole) of acetyl chloride were slowly added over a 15 minute period and refluxing was continued While using a CaCl tube to exclude moisture. After refluxing for an hour, an additional 50 ml. of acetyl chloride was added and refluxing was continued for another 15 hours. The mixture was then cooled, decanted from the sludge and evaporated dry. The residue was redis solved in about 250-350 ml. of benzene, the solution filtered, and the filtrate poured into 3 1. of hexane. The resulting pink precipitate was filtered off and dried to yield 22.5 g. of the acetyl derivative, a pink solid melting at -1 15 C., 22.5 g. (.0246 mole) of the acetyl derivative was dissolved in 250 ml. of methyl Cellosolve at room temperature and the mixture was brought to reflux under a blanket of nitrogen. A deaerated solution of 10 g. (.179 mole) of potassium hydroxide in 20 ml. of water was added dropwise to the refluxing solution under nitrogen over a period 3 to 5 minutes and the reflux was then continued for an additional 10 to 15 minutes. The solution was then allowed to cool, poured quickly into excess dilute hydrochloric acid to form a precipitate which Was filtered ofi, rinsedand dried. The precipitate was then crystallized from methyl Cellosolve to yield 4.6 g. of a dark purple solid, 3-[4 3- (2",5 dihydroxyphenyl) ethyl] phenyl 6 [4 p- (2",5" dihydroxyphenyl) ethyl] anilino anthrapyridone, which melted at 256-258 C., was soluble in pyridine, dimethyl formamide and dilute alkali, and has the following structural formula:

Spectral analysis of the product showed a A in methyl Cellosolve=532 mp; e=12,300.

Example 3 A mixture of 27 g. (.95 mole) of l,4-bis-[;8-( 2',5'- dihydroxyphenyl) 0c methyl] ethylamino anthraquinone and 62 ml. (.87 mole) of acetyl chloride were refluxed on a steam bath for 3 /2 hours, cooled, filtered, and then precipitated into 3 l. of hexane. The resulting red precipitate was filtered ofl, rinsed with hexane and air dried. 7.92 g. of the dry precipitate was refluxed under a blanket of nitrogen in 50 ml. of methyl Cellosolve. A nitrogen-deaerated solution of 5.6 g. (.1 mole) of potassium hydroxide in 20 ml. of methyl Cellosolve and ml. of Water was added under nitrogen over a period of 3 minutes. Reflux was then continued for an additional 7 minutes, after which the solution was cooled for 20 minutes and ml. of acetic acid was added. The solution was then poured into 1 l. of dilute acetic acid to precipitate out a magenta solid, which was filtered off and dried to yield 6.1 g. of crude product. Purification by chromatography yielded 1.55 g. of 3-[;8-(2,5'- dihydroxyphenyl) a methyl] ethyl 6 [/3 (2,5- dihydroxyphenyl) oz methyl] ethylamino anthrapyridone, having the following structural formula:

and a spectral absorption curve in methyl Cellosolve exhibiting absorption maxima at 542 and 510 mg; e=12,200.

Example 4 A mixture of 24 .0 g. (.10 mole) of quinizarin, 60.0 g. (.226 mole) of amino-phenethyl-hydroquinone hydrochloride, 12.4 g. (.20 mole) of sodium bicarbonate and 21.0 g. of boric acid in 250 ml. of pyridine was refluxed under nitrogen for about 48 hours until no further change in the visible spectrum was observed. The mixture was then cooled under an atmosphere of nitrogen and filtered. The filtrate was poured into a large volume of an excess of cold dilute hydrochloric acid with vigorous stirring. The precipitate was filtered 0E and dried to yield 43 g. of 4-[4'-B-(2",5-dihydroxyphenyl)-ethyl]-anilinol-hydroxy-anthraquinone, having the following structural formula:

| Nn @om on I OK A mixture of 20.0 g. (.0443 mole) of the above compound, 14.84 g. (.060 mole) of fi-(LS-dihydroxyphenyD- a-methyl-ethylamine hydrobromide, 5.13 g. (.061 mole) of sodiom bicarbonate, and 200 ml. of methyl Cellosolve was refluxed under a blanket of nitrogen, thereby evolving carbon dioxide gas. When the evolution of gas ceased, 10 ml. of acetic acid was added and refluxing was continued for 24-48 hours until no further change in the visible spectrumwas observed. The mixture was then cooled under nitrogen, filtered, and the filtrate poured into a large volume of colddilute hydrochloric acid with vigorous stirring. The resulting precipitate was filtered off and vacuum dried to yield a crude product, 1 [,8 (2,5 dihydroxyphenyl) a methyl] ethyl- 12 amino 4 [4' ,9 (2",5" dihydroxyphenyl) ethyl]- anilino-anthraquinone of the following structural formula:

(llHa IIIH-CHCH2 on II I o Nrr -orn-orr I on The last-mentioned product was purified by precipitation into hexane from ethyl acetate solution followed by repeated extractions in acetone and evaporations until dry, until 8 g. of purified product was recovered. 6.5 g. of the purified product (.0108 mole), 23 ml. (.324 mole) of acetyl chloride and 270 ml. of dry benzene were refluxed together on a steam bath for about 24 hours until the A of the solution was about 500 m The solution was then cooled and filtered and the residue was rinsed with benzene. The rinsings were also filtered and the filtrates were then combined and precipitated into about 3 l; of hexane. The precipitate was filtered off and vacuum dried to yield 6.7 g. of acetylated anthraquinone product. 4 g. of this product was refluxed in 40 ml. of methyl Cellosolve under a blanket of nitrogen. A deaer ated solution of 3.92 g. (0.7 mole) of potassium hydroxide in 4 ml. of water was then added under nitrogen during a one mintue period. The reflux was continued for another 4 minutes, then the mixture was cooled, acidified with acetic acid and precipitated into cold dilute hydrochloric acid with vigorous stirring. The precipitate was then filtered and dried to yield 3.2 g. of crude product. Purification by chromatography gave two separate fractions: (1) 3-[fi-(2',5-dihydroxyphenylyet-methyl]-ethyl- 6-[4-/3-(2,5"-dihydroxyphenyl ethyl] anilinoanthrapyridone, having the following structural formula:

and (2) 3-[4'48-(2,5"dihydroxyphenyl)-ethyl]-phenyl- 6-[5 (2-5'-dihydroxyphenyl)-a-methyl]-ethylamino-anthrapyridone, having the following structural formula:

(IJH.

wise indicated, are: Example A photosensitive element is prepared by coating a gelatin coated film base with a solution comprising:

G. Acetone 50 Tetrahydrofuran 50 Cellulose acetate hydrogen phthalate 4 1-acetyl-3-18-(2',5'-dihydroxyphenyl)-ethyl- 6 [3-(2',

5'-dihydroxyphenyl)-ethylarnino-anthrapyridone 3.8 After this coating has dried, a silver iodobromide emulsion is applied. The photosensitive element is exposed and an aqueous liquid processing composition comprismg:

Percent Sodium carboxymethyl cellulose 4.5 l-phenyl-B-pyrazolidone 0.2 Sodium hydroxide 2.0 Potassiumbromide 0.2

is spread between the exposed photosensitive element and an image-receiving element as said elements are brought into superposed relationship. The image-receiving ele- .ment comprises a cellulose acetate-coated baryta paper which has been coated with a 6% aqueous polyvinyl alcohol solution. After an imbibition period of approximately one minute, the image-receiving element is separated and is found to contain a reddish-pink, positive image of the photographed subject matter.

Example 6 position comprising: Perwnt Sodium carboxymethyl cellulose 4.5 Potassium bromide 0.2 Sodium hydroxide 1.5 1-phenyl-3-pyrazolidone 0.2

gives a magenta, positive image on a superposed imagereceiving element prepared as described in Example 2.

Example 7 A photosensitive element was prepared by coating 3. gelatin subcoated cellulose acetate film base with a solution comprising 0.25 g. of 3-[/3-(2',5-dihydroxyphenyl)- a-methyH-ethyl 6 [4' B (2-5"-dihydroxyphenyl)- ethyl]-anilino-anthrapyridone, dissolved in 10 cc. of a solution of 4% cellulose acetate hydrogen phthalate in a 50:50 mixture, by volume, of methanol and tetrahydrofuran. After this coating dried, a green-sensitive silver iodobromide emulsion was applied and allowed to dry. This photosensitive element was exposed and brought into superposed relationship with an image-receiving element as an aqueous composition comprising:

Water cc 100 NaOH g 5.17 Hydroxyethyl cellulose (high viscosity) [commercially available from Hercules Powder Co., under the trade name Natrosol 250] g 4.03 Sodium thiosulfate g 1.15 Benzotriazole g 2.3 N-benzyl-a-picolinium bromide g 2.3

NaOH Hydroxyethyl cellulose (high viscosity) [commer- 14 was spread between said elements. The image-receiving element comprised a 2:1 mixture by weight of polyvinyl alcohol and poly-4-vinylpyridine on a baryta paper support. After an imbibition period of approximately one minute, the image-receiving element was separated and contained a magenta positive image.

Example 8 A photosensitive element was prepared by coating a gelatin subcoated cellulose acetate film base with a solu tion comprising 0.49 g. of 3-[4H8-(2,5-dihydroxyphenyl)-ethyl]-phenyl- 6 3-(2',5' dihydroxyphenyD-umethyl]-ethylamino-anthrapyridone, dissolved in 10 cc. of a solution of 2% cellulose acetate hydrogen phthalate in a 50:50 mixture, by volume, of acetone and tetrahydrofuran. After this coating dried, a green-sensitive silver iodobromide emulsion was applied and allowed to dry. This photosensitive element was exposed and brought into superposed relationship with an image-receiving element as an aqueous composition comprising:

Water cc g 3.0

cially available from Hercules Powder Co., under trade name Natrosol 250] g 3.5 Sodium thiosulfate g 1.2 .Benzotriazole g 1.5 N-benzyl-a-picolinium bromide g 2.3

was spread between said elements. The image-receiving element comprised a 2:1 mixture by weight of polyvinyl alcohol and poly-4-vinylpyridine on a baryta paper support. After an imbibition period of approximately one minute, the image-receiving element was separated and contained a magenta positive image.

It will be appreciated that the dye developers may, for example, be dispersed in a layer of gelatin in lieu of the procedures described in the aforementioned photo graphic examples. This dispersion may be made by procedures known in the art. For example, the dispersion may be made by dissolving the dye developer in a suitable organic solvent or mixture of solvents and agitating this solution in a Waring Blendor with an aqueous gelatin solution and a suitable dispersing agent. The resulting dispersion may be diluted, if desired, and coated onto a gelatin subcoated film base in the manner heretofore described.

The dye developers of this invention are also useful in integral multilayer photosensitive elements for use in multicolor diffusion transfer processes. As an example of such photosensitive elements, mention may be made of the photosensitive elements disclosed and claimed in the copending US. application of Edwin H. Land and Howard G. Rogers, Serial No. 565,135, filed February 13, 1956, wherein at least two selectively sensitized photosensitive strata are superposed on a single support and are processed, simultaneously and without separation, with a single common image-receiving element. A suitable arrangement of this type comprises a support carrying a redsensitive silver halide emulsion stratum, a green-sensitive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum, said emulsions having associated therewith, respectively, a cyan dye developer, a magenta dye developer and a yellow dye developer. In one of the preferred embodiments of photosensitive elements of this type, the dye developers are disposed in separate alkali-permeable layers behind the photosensitive silver halide emulsion stratum with which they are associated.

The photosensitive elements within the scope of this invention may be used in roll film units which contain a plurality of photosensitive frames. The photosensitive elements of this invention are especially useful in composite roll film intended for use in a Polaroid Land Camera, sold by Polaroid Corporation, Cambridge 39, Massachusetts, or a similar camera structure such, for

example, as the camera forming the subject matter of US. Patent No. 2,435,717, issued to Edwin H. Land on February 10, 1948. In general, such composite roll films comprise a photosensitive roll, a roll of image-receiving material and a plurality of pods containing an aqueous alkaline processing solution. The rolls and pods are so associated with each other that, upon processing, the photosensitive element may be superposed on the imagereceiving element and the pods may be ruptured to spread the aqueous alkaline processing solution between the superposed elements. The nature and construction of the pods used in such units are well known to the art. See, for example, U.S. Patents Nos. 2,543,181 and 2,634,886, issued to Edwin H. Land.

It will be noted that the liquid processing composition may contain one or more auxiliary or accelerating silver halide developing agents, such as p-methylaminophenol (Metol); 2,4-diaminophenol (Amidol); benzylaminophenol; hydroquinone; a substituted hydroquinone such as toluhydroquinone, phenylhydroquinone, or 4-methylphenylhydroquinone; or a 3-pyrazolidone such as 1- phenyl-3-pyrazolidone. These silver halide developing agents are substantially colorless, at least in their unoxidized form. It is possible that some of the dye developer oxidized in exposed areas may be oxidized by an energy transfer reaction with oxidized auxiliary de veloping agent.

In addition, development may be effected in the presence of an onium compound, particularly a quaternary ammonium compound, in accordance with the processes disclosed and claimed in the copending application of Milton Green and Howard G. Rogers, Serial No. 50,851, filed August 22, 1960.

The dye developers of this invention may be used also in conventional photographic processes, such as tray or tank development of conventional photosensitive films, plates or papers to obtain black-and-white, monochromatic or toned prints or negatives. By way of example, a developer composition suitable for such use may comprise an aqueous solution of approximately 1-2% of the dye developer, 1% sodium hydroxide, 2% sodium sulfite and 0.05% potassium bromide. After development is completed, any unreacted dye developer is washed out of the photosensitive element, preferably with an alkaline washing medium or other medium in which the unreacted dye developer is soluble. The expression toned is used to designate photographic images wherein the silver is retained with the precipitated dye, whereas monochromatic is intended to designate dye images free of silver.

It should be noted that the dye developers of this medium are self-sufficient to provide the desired color image and do not depend upon coupling reactions to produce the desired color. They thus provide a complete departure from conventional photographic color processes in which the color is produced by a coupling reaction between a color former or coupler and the oxidized developing agent, as well as so-called autocoupling processes in which color is obtained by a reaction of the oxidized developing agent with unoxidized developing agent.

It will be apparent that, by appropriate selection of the image-receiving element from among suitable known opaque and transparent materials, it is possible to obtain either a colored positive reflection print or a colored positive transparency. Likewise, the inventive concepts herein set forth are adaptable for multicolor work by the use of special photographic materials, for example, film materials of the type containing two or more photosensitized elements associated with an appropriate number of image-receiving elements and adapted to be treated with one or more liquid processing compositions, appropriate dye developers suitable to impart the desired subtractive colors being incorporated in the photosensitized elements or in the liquid processing compositions. Examples of 18 such photographic materials are disclosed in US. Patent No. 2,647,049 to Edwin H. Land.

As examples of useful image-receiving materials, men tion may be made of nylon, e.g., N-methoxymethyl-polyhexamethylene adipamide, polyvinyl alcohol, and gelatin, particularly polyvinyl alcohol or gelatin containing a dye mordant such as poly-4-vinylpyridine. The image-receiving element also may contain a development restrainer, e.g., l-phenyl-5-mercaptotetrazole, as disclosed in the copending application of Howard G. Rogers and Harriet W. Lutes, Serial No. 50,849, filed August 22, 1960.

The dye developers herein set forth are also useful in the formation of colored images in accordance with the photographic products and processes described and claimed in US Patent No. 2,968,554, issued to Edwin H. Land on January 17, 1961.

The novel compounds herein disclosed are also suitablef or use as dyes for textile fibres, such as nylon.

In the preceding portions of the specification, the expression color has been frequently used. This expression is intended to include the use of a plurality of colors to obtain black.

This application is in part a continuation of our copending application, Serial No. 799,485, filed March 16, 1959, which in turn is in part a continuation of application Serial No. 522,848, filed July 18, 1955, and now abandoned.

Our copending US. application Serial No. 150,661, filed concurrently herewith, now US. Patent No. 3,076,808, claims the novel compounds of the present invention and processes for the preparation thereof.

Since certain changes may be made in the above products, compositions and processes without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

What is claimed is:

1. A photographic developer composition comprising an aqueous alkaline solution containing at least one accelerating silver halide developing agent which is substantially colorless in at least its unoxidized form and an anthrapyridone dye, at least one of the 3 and 6 position nuclear carbon atoms of the anthrapyridone nucleus having linked thereto a substituent having a group of the formula:

wherein: Y is a divalent organic linking group selected from the group consisting of lower alkylene, phenylene and lower alkyleneradicals; and Z is an aryl nucleus selected from the group consisting of benzene and naphthalene nuclei substituted by at least two groups selected from the group consisting of hydroxyl and amino groups, at least one of said groups being substituted in one of the ortho and para positions with respect to the other of said groups, so as to be capable of developing an exposed silver halide emulsion.

2. A photographic developer composition comprising an aqueous alkaline solution containing at least one accelerating silver halide developing agent which is substantially colorless in at least its unoxidized form and an anthrapyridone dye of the formula:

17 wherein R is selected from the group consisting of hydrogen and acetyl; R is selected from the group consisting of hydrogen, lower alkyl and --Y--Z; R is selected from the group consisting of hydrogen and --Y-Z; Y is a divalent organic linking group selected from the group consisting of lower alkylene, phenylene, and

lower alkyleneradicals; Z is an aryl nucleus selected from the group consisting of benzene and naphthalene nuclei substituted by two groups selected from the group consisting of hydroxyl and amino groups, one of said groups being substituted in one of the ortho and para positions with respect to the other of said groups so as to be capable of developing an exposed silver halide emulsion and at least one of said R and R is Y-Z.

3. A photographic developer composition comprising an aqueous alkaline solution containing at least one accelerating silver halide developing agent which is substantially colorless in at least its unoxidized form and l-acetyl-3-B- 2',5 '-dihydroxyphenyl) ethyl-6-fl- (2,5 dihydroxyphenyl)-ethylamino-anthrapyridone.

4. A photographic developer composition comprising an aqueous alkaline solution containing at least one accelerating silver halide developing agent which is substantially colorless in at least its unoxidized form and 3-[fl-(2',5'-dihydroxyphenyl)-a-methyl]-ethyl-6-[5 (2', 5-dihydroxyphenyl)-a-methyl]ethylamino anthrapyridone.

5. A photographic developer composition comprising an aqueous alkaline solution containing at least one accelerating silver halide developing agent which is substantially colorless in at least its unoxidized form and 3-[fl-(2,5'-dil1ydroxyphenyl)a-methyl]-ethyl-6-[4' )8- (2",5 "-dihydroxyphenyl) ethyl] anilino-anthrapyridone.

6. A photographic developer composition comprising an aqueous alkaline solution containing at least one accelerating silver halide developing agent which is substantially colorless in at least its unoxidized form and 3 [4-fl-(2",5"-dihydroxyphenyl) ethyl] phenyl-6- [a (2, 5'-dihydroxyphenyl)-ct-methyl]-ethylamino anthrapyridone.

7. A photographic developer composition comprising an aqueous alkaline solution containing at least one accelerating silver halide developing agent which is substantially colorless in at least its unoxidized form and 3-[4'-fi-(2",5"-dihydroxyphenyl)ethyl]-phenyl-6-[4 [3- (2",5-dihydroxyphenyl) ethyl] anilino-anthrapyridone.

8. A process for developing an exposed silver halide emulsion which comprises contacting said emulsion with an aqueous alkaline solution of an anthrapyridone dye, at least one of the 3 and 6 position nuclear carbon atoms of the anthrapyridone nucleus having linked thereto a substituent having a group of the formula:

wherein: Y is a divalent organic linking group selected from the group consisting of lower alkylene, phenylene and lower alkyleneradicals; and Z is an aryl nucleus selected from the group consisting of benzene and naphthalene nuclei substituted by at least two groups selected from the group consisting of hydroxyl and amino groups, at least one of said groups being substituted in one of the ortho and para positions with respect to the other of said groups, so as to be capable of developing an exposed silver halide emulsion.

9. A process for developing an exposed silver halide emulsion which comprises contacting said emulsion with an aqueous alkaline solution of an anthrapyridone of the formula:

from the group consisting of lower alkylene, phenylene, and

lower alkyleneradicals; Z is an aryl nucleus selected from the group consisting of benzene and naphthalene nuclei substituted by two groups selected from the group consisting of hydroxyl and amino groups, one of said groups being substituted in one of the ortho and para positions with respect to the other of said groups so as to be capable of developing an exposed silver halide emulsion and at least one of said R and R is -Y-Z.

10. A process for developing an exposed silver halide emulsion which comprises contacting said emulsion with an aqueous alkaline solution of l-acetyl-3-fi-( 2',5'-dihydroxyphenyl)-ethyl 6 13 (2,5'-dihydroxyphenyl)ethylamino-anthrapyridone.

11. A process for developing an exposed silver halide emulsion which comprises contacting said emulsion with an aqueous alkaline solution of 3-[fi-(2',5'-dihydroxymethyl] ethylamino-anthrapyridone.

14. A process for developing an exposed silver halide emulsion which comprises contacting said emulsion with an aqueous alkaline solution of 3-[4-/3-(2,5-dihydroxyphenyl) ethyl] phenyl-6-[4-fi-(2",5"-dihydroxyphenylethyl]anilino-anthrapyridone.

15. In a process of forming photographic images in color, the steps which comprise developing an exposed silver halide emulsion with an aqueous alkaline solution of an anthrapyridone dye, at least one of the 3 and 6 position nuclear carbon atoms of the anthrapyridone nucleus having linked thereto a substituent having a group of the formula:

wherein: Y is a divalent organic linking group selected from the group consisting of lower alkylene, phenylene and mi-lower alkyleneradicals; and Zis an aryl nucleus selected from the group consisting of benzene and naphthalene nuclei substituted 19 by at least two groups selected from the group consisting of hydroxyl and amino groups, at least one of said groups being substituted in one of the ortho and para positions with respect to the other of said groups, so as to be capable of developing an exposed silver halide emulsion; thereby providing in said emulsion a predetermined distribution of unoxidized anthrapyridone dye, and transferring at least part of said distribution of unoxidized dye by imbibition from said emulsion to an image-receiving element in superposed relationship with said emulsion to impart to said image-receiving element a positive dye image of the developed image.

16. The process as defined in claim 15, wherein said anthrapyridone dye is disposed, prior to exposure, in a photosensitive element comprising said silver halide emulsion, and the solution containing said dye is formed by permeating said photosensitive element with an aqueous alkaline solution capable of solubilizing said dye.

17. The process as defined in claim 15, wherein said solution is introduced by being spread in a substantially uniform layer between said photosensitive element and said image-receiving element as said elements are brought into superposed relationship.

18. In a process of forming photographic images in color, the steps which comprise developing an exposed silver halide emulsion with an aqueous alkaline solution of an anthrapyridone of the formula:

lower alkyleneradicals; Z is an aryl nucleus selected from the group consisting of benzene and naphthalene nuclei substituted by two groups selected from the group consisting of hydroxyl and amino groups, one of said groups being substituted in one of the ortho and para positions with respect to the other of said groups so as to be capable of developing an exposed silver halide emulsion and at least one of said R and R is -Y--Z; thereby providing in said emulsion a predetermined distribution of unoxidized anthrapyridone dye, and transferring at least part of said distribution of unoxidized dye by imbibition from said emulsion to an image-receiving layer in superposed relationship with said emulsion to impart to said imagereceiving layer a positive dye image of the developed image.

19. In a process of forming photographic images in color, the steps which comprise developing an exposed silver halide emulsion with an aqueous alkaline solution of 1-acetyl-3-fi-(2',5'-dihydroxyphenyl)-ethy1-6-fl-(2',5'-dihydroxyphenyl)-ethylamino-anthrapyridone; thereby providing in said emulsion a predetermined distribution of unoxidized anthrapyridone dye, and transferring at least part of said distribution of unoxidized dye by imbibition from said emulsion to an image-receiving layer in superposed relationship with said emulsion to impart to said image-receiving layer a reversed, positive dye image of the developed image.

, 20. In a process of formingphotographic images in color, the steps which comprise developing an exposed silver halide emulsion with an aqueous alkaline solution of 3-[B-(2,5'-dihydroxyphenyl) oz methyl]-ethyl-6-[fi (2',5'-dihydroxyphenyl) a methyl]-ethylamino-anthrapyridone; thereby providing in said emulsion a prcdeter mined distribution of unoxidized anthrapyridone dye, and transferring at least part of said distribution of unoxidized dye by imbibition from said emulsion to an image-receiving layer in superposed relationship with said emulsion to impart to said image-receiving layer a reversed, positive dye image of the developed image.

21. In a process of forming photographic images in color, the steps which comprise developing an exposed silver halide emulsion with an aqueous alkaline solution of 3 [,8 (2' 5' dihydroxyphenyl) a methyl] -ethyl- 6 [4' s (2",5" dihydroxyphenyl) ethyl] anilinoanthrapyridone; thereby providing in said emulsion a predetermined distribution of unoxidized anthrapyridone dye, and transferring at least part of said distribution of unoxidized dye by imbibition from said emulsion to an image-receiving layer in superposed relationship with said emulsion to impart to said image-receiving layer a reversed, positive dye image of the developed image.

22. In a proces of forming photographic images in color, the steps which comprise developing an exposed silver halide emulsion with an aqueous alkaline solution of 3 [4-;9(2",5-dihydroxyphenyl)-ethyl] -phenyl-6-[fl- (2',5' dihydroxyphenyD-a-methyl] ethylamino-anthrapyridone; thereby providing in said emulsion a predetermined distribution of unoxidized anthrapyridone dye, and transferring at least part of said distribution of unoxi dized dye by imbibition from said emulsion to an imagereceiving layer in superposed relationship with said emulsion to impart to said image-receiving layer a reversed, positive dye image of the developed image.

23. In a process of forming photographic images in color, the steps which comprise developing an exposed silver halide emulsion with an aqueous alkaline solution of 3 [4'-,B-(2,5"-dihydroxyphenyl)-ethyl]-phenyl-6-[4- )3 (2",5" dihydroxyphenyl) ethyl] anilino anthrapyridone; thereby providing in said emulsion a predetermined distribution of unoxidized anthrapyridone dye, and transferring at least part of said distribution of unoxidized dye by imbibition from said emulsion to an image-receiving layer in superposed relationship with said emulsion to impart to said image-receiving layer a reversed, positive dye image of the developed image.

24. A photographic product comprising a support, a silver halide emulsion located in a layer on said support, and a dye developer located in a layer on the same side of said support as said emulsion, said dye developer comprising an anthrapyridone dye, at least one of the 3 and 6 position nuclear carbon atoms of the anthrapyridone nucleus having linked thereto a substituent having a group of the formula:

wherein: Y is a divalent organic linking group selected from the group consisting of lower alkylene, phenylene and lower alkylcneradicals; and Z is an aryl nucleus selected from the group consisting of benzene and naphthalene nuclei substituted by at least two groups selected from the group consisting of hydroxyl and amino groups, at least one of said groups being substituted in one of the ortho and para positions with respect to the other of said groups, so as to be capable of developing an exposed silver halide emulsion.

25. A photographic product comprising a support, a silver halide emulsion located in a layer on said support, and a dye developer located in a layer on the same side 21 of said support as said emulsion, said dye developer comprising an anthrapyridone dye of the formula:

( NH-R wherein R is selected from the group consisting of hydrogen and acetyl; R is selected from the group consisting of hydrogen, lower alkyl and --Y-Z; R is selected from the group consisting of hydrogen and -YZ; Y is a divalent organic linking group selected from the group consisting of lower alkylene, phenylene, and

lower alkyleneradicals; Z is an aryl nucleus selected from the group consisting of benzene and naphthalene nuclei substituted by two groups selected from the group consisting of hydroxyl and amino groups, one of said groups being substituted in one of the ortho and para positions with respect to the other of said groups so as to be capable of developing an exposed silver halide emulsion and at least one of said R and R is -Y-Z.

26. A photographic product comprising a support, a silver halide emulsion located in a layer on said support, and 1-acetyl-3-fi-(2,5-dihydroxyphenyl)ethyl-6-fl-(2,5'- dihydroxyphenyl)-ethylamino-anthrapyridone located in a layer on the same side of said support as said emulsion.

27. A photographic product comprising a support, a silver halide emulsion located in a layer on said support, and 3 [fi-(2,5-dihydroxyphenyl)a-methyl]-ethyl-6-[fi (2',5 dihydroxyphenyl) a-methyl] ethylamino-anthrapyridone located in a layer on the same side of said support as said emulsion.

28. A photographic product comprising a support, a silver halide emulsion located in a layer on said support, and 3 [fl-(2',5-dihydroxyphenyl)-a-methyl]-ethyl-6-[4'- 5 (2,5" dihydroxyphenyl) ethyl] anilino-anthrapyridone located in a layer on the same side of said support as said emulsion.

29. A photographic product comprising a support, a silver halide emulsion located in a layer on said support, and 3- [4-5- 2",5 "-dihydroxyphenyl) ethyl] -phenyl-6-[ 8- (2',5' dihydroxyphenyl)-a-methyl] ethylamino-anthrapyridone located in a layer on the same side of said support as said emulsion.

30. A photographic product comprising a support, a silver halide emulsion located in a layer on said support, and 3 [4-B-(2",5" dihydroxyphenyl)-ethyl]-phenyl-6- [4-}8-(2,5" dihydroxyphenyD-ethyl] aniline-anthrapyridone located in a layer on the same side of said support as said emulsion.

References Cited in the file of this patent UNITED STATES PATENTS 2,268,814 Frame Jan. 6, 1942 2,983,606 Hogers May 9, 1961 FOREIGN PATENTS 664,270 Great Britain Jan. 2, 1952 OTHER REFERENCES Venkataraman: Synthetic Dyes, Academic Press, New York, pp. 358-857; 1210-1227. 

15. IN A PROCESS OF FORMING PHOTOGRAPHIC IMAGES IN COLOR, THE STEPS WHICH COMPRISE DEVELOPING AN EXPOSED SILVER HALIDE EMULSION WITH AN AQUEOUS ALKALINE SOLUTION OF AN ANTHRAPYRIDONE DYE, AT LEAST ONE OF THE 3 AND 6 POSITION NUCLEAR CARBON ATOMS OF THE ANTHRAPYRIDONE NUCLEUS HAVING LINKED THERETO A SUBSTITUENT HAVING A GROUP OF THE FORMULA: 